CH628924A5 - PHOTOGRAPHIC IMAGE FORMING COMPOUNDS. - Google Patents

Description

The invention relates to novel image-forming compounds in photographic products. The compounds according to the invention contain releasable groups which are dye-forming groups or photographic reagents. These compounds are acceptors of at least one electron, which causes an intramolecular nucleophilic rearrangement before the groups are released.

Belgian patent 810 195 describes intramolecular nucleophilic rearrangement compounds containing a hydroxylamino nucleophilic group which are used in photographic products to release a diffusible dye-forming group or a photographic reagent.

It has been found, according to the invention, compounds which give rise to an intramolecular nucleophilic rearrangement, and which offer certain advantages when used in photographic products, as regards the possibility of controlling the release of a formation group of dye or photographic reagent. The compounds according to the invention are aromatic nitro compounds which, being electron acceptors (with reduction), give rise to an intramolecular nucleophilic rearrangement so as to release a dye image-forming group or a photographic reagent.

The compounds useful according to the invention are nitro aromatic compounds containing at least one other group, in the aromatic nucleus or as a substituent of the aromatic nucleus,

15

20

30

35

(I)

/.CR2).—1—- v / —r>

Vr - p-i A

in which A represents the atoms necessary to complete a mono- or polycyclic aromatic or hetero-aromatic group, the ring of which carries the nitro radical is penta-gonal or hexagonal; including structures with several aromatic or heteroaromatic rings and in which the rings can be carbocyclic or heterocyclic, such as the groups containing aromatic onium radicals in the ring, A advantageously represents the radicals necessary to form a carbocyclic ring, such than a benzene or naphthalene ring; W represents an electron acceptor group whose value of the Hammet sum is positive and includes radicals such as cyano, nitro, fluoro, bromo, iodo, trifluoromethyl, trialkylammonium, carbonyl, carbamoyl substituted on nitrogen, sulfoxide , sulfonyl or sulfamoyl substituted on nitrogen, or groups of esters; R2 represents a hydrogen atom, an substituted or unsubstituted alkyl radical, advantageously containing 1 to 30 carbon atoms, or a substituted or unsubstituted aryl radical, advantageously containing 6 to 30 carbon atoms; R1 represents a bivalent organic radical containing 1 to 3 atoms in the bivalent linking chain and can represent the

50

55

60

65

such as an electron accepting group. When these compounds are used in photography, at least one of the cycle substituents comprises a dye image-forming group or a photographic reagent separated from the cycle by an electrophilic group giving rise to a cleavage which comprises an electrophilic center and a group released. The released group is capable of being split by intramolecular nucleophilic rearrangement as a result of the reduction of the nitro group.

According to the invention, liberable groups have been found which can be placed on any molecule via a bonding atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or an atom. selenium. Releasable groups can be used to control the time and speed with which they are released from the compound.

The compounds according to the invention offer several advantages. For example, reduction can be accomplished prior to intramolecular nucleophilic rearrangement by organic reducing agents under conditions encountered in many photographic development processes. In contrast, according to previous publications, the aromatic nitro compounds are reduced by hydrogenation in the presence of a catalyst such as a noble metal.

The compounds according to the invention have the following formula:

- (R '

alkylene, oxaalkylene, thioalkylene, aminoalkylene radicals, nitrogen atoms substituted by an alkyl or aryl radical; m and ç [

are 1 or 2; £ is an integer equal to or greater than 1

and preferably equal to 3 or 4 when [(R2) - - - W] represents q 1

a substituent placed at any point in the aromatic structure of A, p is equal to 1 only when A contains an aromatic onium radical and when £ is equal to 2, [(R2 - - W]

is in the ortho or para position relative to the nitro radical; E and Q form an electrophilic releasable group where E represents an electrophilic center which is preferably a carbonyl radical including a carbonyl (-CO-) and thiocarbonyl (-CS-) radical, or else it represents a sulfonyl group, Q represents a group forming a monoatomic link chain between E and X1, Q represents an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom which makes it possible to obtain an amino radical, and advantageously , Q represents an amino radical in which the alkyl substituent contains from 1 to 20 atoms and preferably from 1 to 10 carbon atoms, including a substituted alkyl radical, Q can represent the atoms necessary for

628,924

4

form with X1, a ring of 5 to 7 atoms, such as a radical in which, E, Q and X1 conform to the definitions given

pyridino or piperidino; n is equal to 1,2 or 3 and, advantageous.

ment, is equal to 1; X1 considered with Q, represents either a In general, the compounds according to the invention are a dye image-forming group, such as a dye for the precursors of compounds which play a role of compounds or a precursor for a dye, or a group of a reagent 5 undergoing an intramolecular nucleophilic rearrangement in the photographic, such as an anti-veil, a solvent for the halides in the photographic product. The nitro radical of the compound gives silver, a tone-modifying agent, a fixing agent, which is reduced to form a nucleophilic group. The ex-

a development accelerator compound, a developer, pressure "intramolecular nucleophilic rearrangement" is related

a tanning agent or a development inhibitor. leads to a mechanism in which part of the molecule

When multiple groups are present in the compound, 10 is actually rearranged and not simply arranged elsewhere.

as represented in the formula above, it should be noted that they are on the molecule; that is, the electrophilic center must be the same or different. For example, when g is able to form a cyclic structure with such a group

equal to 3, each [(R2 W] can be chosen from the different nucleophiles. In the compounds according to the invention, the ra-

1 ~ 1. . _ dical nitro of the aromatic cycle becomes a nucleophilic substituent group as indicated. It should be noted that the radical R 15 after its reduction; that is to say after having captured at least one can be attached to all electron or electron accepting groups. The intramo-only nucleotide rearrangement compounds on some of them; that is to say when E is lecular are those which have the nucleophilic group and the greater than 2.3 may be equal to 2 on certain groups and equal to 1 electrophilic center juxtaposed in the configuration in three di-on to others groups. Mensions of the molecule, to favor the bringing together of the Form I above, includes compounds in the 2Q group by which the nucleophilic rearrangement reaction which the multiple releasable groups are placed on an intramolecular group can have Ueu. In general, in these dye image-forming or on a photogra- cive reagent, including compounds with several cycles, it is possible to phique, that is to say when n is greater than 1. The compounds of place respective electrophilic and nucleophilic groups, where this class is advantageous if more than one free group is used - the groups have a position making the reaction possible, ble to offset the maximum absorption of a dye for 25 However, the groups nucleophiles and electrophiles are to prevent the reaction of the releasable group or to obtain pIaces> advantageously on compounds in which there are additional adjustments of the diffusion of the group easily deforms an organic cycle or a profusible organic cycle. vision by intramolecular reaction of the nucleophilic group, to

In certain embodiments, and more particularly „, f. , ^ ^ / T f ,,,, r.

,. „„,. j r, ..,. would render or be the electrophilic center. Generally, these in those where Ion uses the compounds in photo-,. _

R2, advantageously, represents a group of the are. ^ .rmeS? 3-7 months and Jav ^

stage which renders the compound immobile and indisputable in con- tents, in accordance with the invention the nucleoplule group and the alkaline treatment ditions and (Q-X1) represents an electrophilic group are placed on a compound or they form diffusely. The nature of the ballasting group is not critical of a key of 5 to 7 atoms and of ference, a cycle of 5 to 6 is only provided that the part of the compound forming part of the group of rings with 4 atoms being generally recognized to be diffi-

ballasting of E, being mainly responsible for immobility. 35 cdfs formed during organic reactions). In compounds generally, when R2 represents a ballasting group, according to an ion, the nucleophilic rearrangement mtramolecu laire

R2 includes the long chain alkyl radicals as well as aheu after Ration of at least one electron by the radical the aromatic radicals of the series of benzene and naphtha- mtro'Avan the r ^ uctlon of, ra ^ ica mtro'la ^ sse de falène. Conventional groups useful as groups of les, which are slow *, so to speak equal to 0 stage, contain from 8 to 30 carbon atoms and preferably 40, we must number q "6,168 salt compounds ° n 1 mention, are stable at least 12 carbon atoms.in processing conditions except when the com-The electron acceptor groups being part of the P °, its sTandent ''> nfquence direct de la reduction of a radi-

posed of formula I, are those which have a value of cal mtro-Les ^ mP ° fs Pfnt co, nten "'d other f> uPe 1U1

Hammet sum which is positive, advantageously greater than 1, onsent or s ty * ° lysent. However, the pnnapale hberation is greater than + 0.2 or the substituents of the aromatic nucleus 45 ^ lon an aheu image by rearrangementnucleophilemtramo-

associated with each other, correspond to a value greater than 0.5. Ocular, when the group nucleophile obtains by reduction of

The values of the Hammet sum are calculated according to the metallcal ar ° ma ^ quf nitro'rea ^ with an electroPhlle center of the methods described in the publication "Steric Effects in Organic group of the compound when the aromati-chemistry compounds" , Publisher John Wiley and Sons, Inc., 1956, pages <n fes f are used in a strong basic environment, it should be noted that 570-574, and in the work "Progress in Physical Organic Che- 50 on choifles. from the erotic comic book nitre de mistry ”, Vol. 2, Publisher: Interscience, 1964, pages 333-339. way to get compounds that are relatively stable in

Used in the description, the expression "aromatic cycle with an emiieu-asic presence.

electron acceptor substituent ”relates to onium radicals. Generally, the nitro radical and the electropresent groups in the ring and the radicals substituted directly on philes are both fixed on the same aromatic structure. The ring which may represent a linkage chain for the 55 structures may be a structure with a carbocyclic ring or other radicals such as the ballast radicals. heterocyclic nucleus and includes rings condensed in

The electron accepting groups include the groups which each group can be on a different cycle. Avanta-intracyclics such as those present in a forging compound, the two groups are linked directly on the mule: same aromatic cycle which is preferably a carbocyte nucleus

60 clicks.

In general, the intramolecular nucleophilic rearrangement compounds obtained by reduction of the compounds

E - Q - x according to the invention, contain 3 to about 5 atoms and before-

(dd) gorely 3 to 4 atoms between the nucleophilic center of the group

65 nucleophile and the atom which forms the electrophilic center, consequently, the nucleophilic center, considered with the center of the electrophilic group, can form a provisional ring or not of 5 to 7 atoms and preferably of 5 or 6 atoms.

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The expression “nucleophilic group” used in the description of hydrolysis to release a group as a function of the pH and the claims which follow, relates to an atom or not and not according to the reduction.

to a group of atoms which has a pair of electrons suitable for In most uses, aromatic compounds form a covalent bond. Groups of this class are nitrated according to the invention, react with a donor compound sometimes ionizable groups which react as groups of electrons which reduces the nitro compound, which makes it possible to obtain anionics. The compounds according to the invention contain ra- a nucleophilic group for the nucleophilic rearrangement of nitro introdicals which give rise to a reduction which allows subsequent obolecular of the releasable group. The compound hold a nucleophilic group such as a hydroxylamino group. electron donor can be supplied to the aromatic compound

The hydroxylamino nucleophilic group may contain more nitrate by spraying, by stencil, by physical transfer, by a nucleophilic center; that is, the nitrogen atom or imbibition or transfer according to an image. The expression "how much the oxygen atom can be the nucleophilic center." When placed electron donor "includes the compounds capable of replus a nucleophilic center is present in the nucleotide group aromatic nitro compounds according to the invention.

phile of intramolecular nucleophilic rearrangement compounds- In photographic products, the

In accordance with the invention, the attack and the rearrangement of nitrated aromatic nucleosides according to the invention in association with phils generally take place, through the center which is the most organic electron donor compounds. In a product capable of forming the most favorable cycle structure. For example, a photograph comprising a layer of arpid halides, if the oxygen atom of the hydroxylamino group can form with which is associated a nitro aromatic compound, there is a 7 atom ring and if the nitrogen atom can form a ring at 6 destroys the electron donor compound in proportion to the atoms, the active nucleophilic center will generally be the atom development of the silver halides. In areas of nitrogen. 20 aunties, the electron donor compound reduces the aro-

The expression “electrophilic group” refers to a nitric atom, allowing the nucleophilic rearrangement in-or to a group of atoms which are capable of accepting a tramolecular pair. When the electron donor compound is electron to form a covalent bond. Elective groups plus a powerful developer of silver halides, the classic pre-trophiles are the sulfonyl radicals (-SO2-), have a higher reaction rate with the halides nyl (-CO-) and thiocarbonyl (- CS-). The carbon atom of silver 25 than with the aromatic nitro compound. Carbonyl radical compounds or the sulfur atom of the sulfonyl radical, useful typical electron donors and which are furthermore

forms the electrophilic center of the group and can carry a group of silver halides comprising the positively charged astable acid. The expression "liberocorbitic electrophilic group, trihydroxypyrimidines such as 2-methyl-ble" used in the description, refers to the group (—EQ -) 4,5,6-trihydroxypyrimidine and hydroxylamines such that where E represents a electrophilic group and Q a liberated group diethylhydroxylamine.

form a monoatomic bond between E and X1 where the atom In photographic products, we can associate the unique is a metalloid whose valence is negative and equal to 2 aromatic nitro compounds according to the invention, with com-or 3 The liberated group is capable of accepting a pair of organic electron donor electrons which are developpers after being moved from the electrophilic group. When the content of the relatively weak or metalloid silver halides is trivalent, it may be mono-substituted by a 35 i do not develop at all.

hydrogen atom, an alkyl radical including radicals In the photographic product, it is possible to incorporate the

substituted alkyl and cycloalkyl or a substituted or posed aryl radical donating electrons in the form of a hydrolysed precursor, or by the atoms necessary to form with X1, a ble cycle, of an immobile compound donor of electrons or d 'a com of 5 to 7 atoms such as a pyridino or piperidino radical. Diffusible electron donor weighing. Generally speaking, examples of atoms useful for forming Q, are the metalloids 40 destroying the electron donor compound according to an image. In groups VB and VIB of the Periodic Table of Beach Elements where it has not been destroyed, it reacts with the compounds and which may have a negative valence of 2 or 3, such aromatic nitro so as to transfer the electrons.

as nitrogen, sulfur, oxygen or selenium atoms. In one embodiment, a photographic product

The compounds according to the invention contain several classes according to the invention contains a nitrated aromatic compound associated with dye-forming groups and photogra- 45 reagents with a precursor of electron donor compound, hydrolysable, phiques which are capable of being released. You can prepare them practically immobile and with an electron transfer agent,

stationary compounds in which the ballast part is released The electron transfer agent, such as a compound 3-pyrazoli-of the diffusible group which can then diffuse towards the layers done, reacts with the developable silver halides for adjacent of the photographic product. A group can be provided with an oxidized electron transfer agent. This compound's agent to produce, for example, an oxidized electron transfer inhibitor then reacts with the developing donor compound. According to a variant, the released group can donate electrons, at the moment when it is made available by hydrolysis, take place with a modification of the resonance such as that of one to destroy a distribution according to an image of the don-dye compound. with maximum absorption offset. In other neur electron modes. The remaining electron donor compound can be produced, a group can be released to allow reaction with the aromatic nitro compound and the latter can be

Compound to undergo subsequent reactions in the phosphor 55 to a reaction with release of a group. When a tographic. diffusible dye is released, it can diffuse to an adjacent image receiving layer.

The compounds according to the invention offer several advantages. The compounds which donate labile electrons in an alkaline medium,

compared to known compounds. These compounds have the advantage that is advantageously used, include the compounds that have the advantage of accepting electrons (that is to say, give rise to a 60 have a limited hydrolysis rate under the conditions of treatment). reduction) before any release has taken place. In addition, the ment and include benzisoxazolones, lactones and compounds remain relatively stable in various blocked hydroquinone media.

such as in alkaline solutions. On the other hand, many - electron donors that can be used in combination -

breux neighboring compounds must be oxidized before giving tion with the aromatic nitro compounds according to the invention, prelieu to a mechanism of release or they must give place 65 feel the following formulas:

h 3000 hd I

h0h! j) ho

1

! o ho-o | 0 = 0 1

ho-o

SZHnDHNZOS

SVW08

ho

09

i-z çç

0Ï

get

9-a zcH8Tqhn2OSzHD ^ HOM € HO

s0-

chd ho oshn hd hooo II 0

i £ h810hnz0szh0zh0neh0

/

0-0

NOT

ho ehd2oshnzhdzhonod hd s-a

<7-3

eeh9i0z0shn

0 hd

0 (zhd) z0shn ^ h8t0

hnoohooodc (ehd)

€ -3

oA8To

Ol z-a

^ eh9tdhnz0szh07hd i £ h81ohnzoszhojhd-n-deh i-a

9

PZ6 SZ9

7

628,924

oh i

ch3 io e-9 oh

20

In certain preferred embodiments of the invention, the liberated group is used as the substituent of a dye with offset maximum absorption to adjust the resonance of the dye. Upon release from the aromatic nitro group, the dye gives rise to a bathochromic or hypsochromic shift. Dyes with offset maximum absorption are known and contain those described in US Pat. No. 3,260,597, in which an acyl radical is used to offset the absorption of the dye. In general, it is possible to use the groups released on any dye 30 comprising a nitrogen atom or an oxygen atom or a sulfur atom or an ionizable selenium atom which influences the resonance of the dye. According to the invention, the group released is a substituent of the dye so that the ionizable group represents the group released in the releasable electrophilic group.

In formula I, group 4 Q-X1) may represent an inhibitor of the development of silver halides, including triazoles and tetrazoles such as 5-mercapto-1-phenyl-tetrazole, 5-methylbenzotriazole or a 4,5-dichlorobenzotri-40 azole. The group can also represent an anti-haze, including an azaindene, such as a tetraazaindene. Compounds that contain inhibitors of the development of silver halides or releasable anti-haze can be combined with the silver halide layers. When the compounds are used in this way, they are incorporated at a rate of 0.1 mg / m2 to 30 mg / m2, in solution in a coupler solvent such as diethyllauramide. When the photographic products contain these compounds in association with negative silver halide emulsions, a positive distribution, according to an image, of the inhibitor or the anti-veil is produced by development. Thus, silver development is inhibited or slowed down at low exposures and not at higher exposures. Thus, inhibition of the development of unexposed areas is selectively obtained. When the silver halide emulsions 55 additionally contain dye-releasing compounds, the overall effect of the inhibitor or antifog is to release a higher content of dye in unexposed areas. This provides improved maximum densities of the dye image for the image receiving layer, without increasing the content of dye released in the exposed areas.

In certain preferred embodiments of the invention, the groups freed are used to ballast a diffusible group forming dye. Preferably, the dye-forming group is a preformed dye or a dye with offset maximum absorption. Dyes of this class are well known and include azo dyes including metallizable and metallized azo dyes, azo-methine (imine) dyes, anthraquinone dyes, alizarin dyes, merocyanines, dyes quinoline and cyanines. The shifted maximum absorption dyes include: compounds whose light absorption characteristics are shifted hypsochrome or bathochrome when subjected to a different environment such as a change in pH, a reaction with a substance to form a complex such as with a metal ion, or the elimination of a group such as a hydrolyzable acyl group bound to an atom of the chromophore compound. The releasable electrophilic group and the other groups in the molecule should be chosen to provide stable compounds when used under very alkaline conditions. Advantageously, the releasable group is linked to an amino radical when the compound is used under very alkaline conditions. In certain embodiments, the dyes with offset maximum absorption are very advantageous and in particular those containing a hydrolyzable radical on an atom affecting the resonance structure of the chromophore group. This preference stems from the fact that these dyes can be incorporated directly into a layer of silver halide emulsion or else incorporated into an adjacent layer, on the exposed face without significantly reducing the exposure to recorded light. After exposure, the maximum absorption of the dye can be shifted to the appropriate color, for example, by removing an acyl radical by hydrolysis, to obtain the respective dye image.

In another embodiment, one uses the releasable groups to provide a temporary ballasting group on a group such as a diffusible dye image precursor. The term "dye image precursor", used in the description, refers to compounds which give rise to reactions such as those which take place in a photographic image forming system and which produce a dye image, such as as couplers or oxychromic compounds.

The nitro aromatic compounds according to the invention have a particular application in a photographic process making it possible to obtain a diffusible group, such as a dye, which is transferred to an adjacent layer or to a receptor element. However, in certain embodiments, the invention relates to the release of an image distribution of a diffusible compound useful in photography such as a photographic reagent. Useful photographic reagents are known and described, for example, in US Patents 3,227,551.3,698,898.3,379,529 and 3,364,022; these photographic reagents can be, for example, a silver complexing agent, a silver halide solvent, a fixing agent, a toning modifying agent, a tanning agent, an anti-haze, a violating agent, a sensitizer, a desensitizer, developer or oxidizing agent. In other words, in formula I, (Q-X1) can represent any group which, associated with a hydrogen atom, releases a photographic reagent. When the photographic reagent is a development inhibitor or an anti-veil, Q advantageously represents a sulfur or active nitrogen atom, such as a benzotri-azole or benzimidazole compound.

Examples of nitro aromatic compounds containing releasable photographic reagents according to the invention have the following formulas:

628,924

8

N M

° 2c12h25

s02c12h25

ch „

0 = c-n-ch-c-n-

2E

ff \

10

15

c12h25s02-

X ÌT2

2v12h25

-sch2ch2cn 20

The diffusible group represented by Q-X1 can represent, moreover, an accelerator of the development of silver halides, such as benzyl alcohol or benzyl-a-picolinium bromide, a veiling agent or nucleating agent , or an auxiliary developer such as 1-phenyl-3-pyrazoli-done, or a solvent for silver halides. In photographic products, when these compounds are combined with silver halide emulsions containing dye imaging compounds according to the invention, the density of the dye released from all dyes in the areas unexposed, is somewhat reduced by the development veil. 35

However, in the photographic product, if one layer is not exposed, while the other two are exposed, the content of fogging agent or of development accelerator compound reaching the unexposed layer via the other two layers must be lower where the layers are exposed. Therefore, the maximum density of the unexposed layer should increase in proportion to the exposure of the other two layers. This significantly increases the saturation of the colors specific to each layer of the photographic product. 45

When couplers are incorporated into the compounds according to the invention, they are released or made available in areas where development does not take place and can react with an oxidized chromogenic developer, such as a primary aromatic amine, to form a dye image. In a general fashion, the coupler and the chromogenic developer are chosen so that the reaction product is immobile. Useful conventional couplers include pyrazolone, pyrazolotriazole, ketomethylenic, open chain and phenolic couplers.

In addition, it is advantageous to use the compounds according to the invention containing oxychromic groups in a photographic process since they are generally colorless due to the absence of a chromophore compound giving an image of dye. Thus, they can be used directly in a photographic emulsion or in a layer placed on the exposure side, without competitive absorption. Compounds of this class give rise to chromogenic oxidation to form the corresponding dye image. Oxidation can be accomplished by subsequent aerial oxidation or by incorporation of oxidants in the image receiving layers of the composite photographic product. Compounds of this class are known as leuco compounds, i.e.

55

compounds that are colorless. Particularly useful and conventional oxychromic compounds include Ieuco-indo-anilines, leuco-indophenols and leuco-anthraquinones.

In the embodiments of the invention for which the nitro aromatic compounds comprising a dye image-forming group, they are usually used in a layer placed on a support in an amount sufficient to obtain a visible image. The necessary content depends on the thickness of the layer and the absorption characteristics of the dye. However, when a visible image is desired, the nitrated aromatic compound is used at a rate of at least 1 × 10 −5 moles / m2 and advantageously from 1 × 10 −4 moles / m2 to 2 × 10 −3 moles / m2.

The compounds according to the invention are particularly useful in photographic products and in photographic methods for obtaining an image distribution of a compound useful in photography. The photographic product may contain a combination of immobile compounds and any photographic recording substance which produces an image distribution of an electron donor compound during development and which in turn can react with the nucleophilic precursor group on the aromatic nitro compound. In certain advantageous embodiments, where silver halide emulsions are used as recording medium, these emulsions can be negative, positive-direct or reversible and give rise to the development by a silver halide developer, so as to produce the oxidized developer. The non-oxidized developer can react with the nucleophilic precursor group by a simple redox reaction or by electron transfer, so as to provide the nucleophilic group, which allows the intramolecular nucleophilic rearrangement of the diffusible group.

Black-white or single-color products can be prepared using a single layer of silver halide emulsion and the compounds according to the invention which include the dye image forming groups necessary to provide the image desired.

Advantageously, the compounds according to the invention are used in three-color systems such as, for example, in photographic products comprising a layer containing a silver halide emulsion sensitive to red, associated with a nitrated aromatic compound containing a formation group d blue-green dye image, a layer containing a green-sensitive silver halide emulsion associated with a nitrated aromatic compound having a magenta dye-forming group, and a layer comprising a sensitive silver halide emulsion blue, associated with a nitrated aromatic compound with an image forming group of yellow dye.

The photographic product is capable of providing an image, either from an image forming group of dye released and become diffusible, or from an immobile dye retained at its initial location. In some cases, both records are used. When using the selected image, the silver and silver halide remaining after development can be removed, if desired, so as to obtain the best properties for the color image.

The photosensitive substances used in the photographic products according to the invention are preferably silver halide emulsions and can comprise silver chloride, silver bromide, silver bromoiodide and silver chlorobromiodide or mixtures of these halides. The emulsions can be coarse or fine grain and can be prepared by well known methods. Surface image emulsions or internal image emulsions can be used. The emulsions can be of regular grains of the class described by Klein and Moisar, in "J. Phot. Sci. " Flight. 12, No. 5. Sept./Oct. 1964, pages 242-251. We can raise awareness

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spectrally the silver halide emulsions by the layers which, in all practical cases, do not migrate through well known methods. The halide emulsions of ar- layers of organic colloid in an alkaline medium, such as the gent prepared by known techniques allowing gelatin to be obtained, in the photographic products according to the invention and a high photographic sensitivity, such as sensitivities advantageously, do not migrate in an alkaline medium having a pH of between 400 ASA and 1000 ASA and even greater than s greater than 11. The same meaning is given to the expression 1000 ASA, are particularly useful in the invention. "motionless". The expression "diffusible" referring to the

It is possible to use mixtures of emulsions having different according to the invention, with the opposite meaning and relating to their different grain sizes and / or different sensitivities so as to be able to diffuse through the colloid layers of products to adjust the contrast. and the latitude of exposure. If desired, photographic in an alkaline medium and in the presence of substances, these emulsions can be applied in the form of separate “indifusible” layers. The expression "mobile" has the same meaning.

These layers may or may not contain an i-forming compound. In the embodiments for which the dye mages are used, particularly when the aromatic nitro colo compounds according to the invention are used in the preformed rants. layers of photographic products, they can be incorporated by

Negative emulsions or emulsions can be used by any known means. Generally, when incorporating positive-direct. 15 nitro, weighted and molecular weight aromatics

In another embodiment, it is possible to apply on a high, in hydrophilic colloids permeable to alkali, support the aromatic compounds nitro in the form of one they are dispersed by suitable methods, such as by layer in a binder permeable to the compounds basic, for the use of solvents.

form, what is usually called a receiving element When using coupler solvents, the image interval. The receptor element can be treated by various useful means of the ratio of the nitro aromatic compound to thode solvent, including that of contacting it face to face with coupler ranges from 1: 3 to 1:10. Preferably, the solvent of the face with the photosensitive element to silver halides, in tear is a moderately polar solvent. Solvents classi-presence of an alkaline solution and a developer of useful haloques include tri-o-cresyl phosphate, silver phthalides. In areas where a di-n-butyl elate donor compound, diethyl lauramide, 2,4-diamylphenol and lectron, such as a silver halide developer not 2s ies liquid dye stabilizers , as described in the arti-oxidized, diffuses towards the receiving layer, the key aromatic compound entitled "Improved Photography Dye Image Stabilizer-Sol-nitro is reduced. If the nitro compound contains a wind group ", Product Licensing Index, Vol. 83, pp. 26-29, March 1971. dye, it provides a permanent recording of the image of In other embodiments, the com-dye can be dissolved in the zones corresponding to the development of the aromatic nitro layers in an organic solvent miscible with original silver halides. After the nucleo-water rearrangement, such as tetrahydrofuran, methyl alcohol, intramolecular phile alcohol, the remainder of ethyl dye, isopropyl alcohol, acetone, 2-butanone, diffusible of the element, for example by washing. By a choice of N-methylpyrrolidone, dimethylformamide, tallow-appropriate dimethyl of the dye image-forming groups, the mixtures of these solvents are oxidized. We can add to this can get a black-white image. In addition, if the compound mixes an appropriate charged polymer latex of the class described nucleophile contains a tanning agent as pho- group in German patent application 2,541,274 and in which graphically useful, it is possible to obtain a record the compounds are distributed over the latex particles.

ment tanned image in areas where the development of In the description, some useful groups are described by silver halides does not take place, that is to say that one obtains reference to the Periodic Table of elements which is a positive image recording if we use a published emulsion pp. 400-401 of the work entitled “Handbook of Che-negative. 40 mistry and Physics ", 39th ed., Chemical Rubber Publishing

Co.

In other embodiments, it is possible to apply uni- Photographic products as described above,

formally the compounds according to the invention on a support. When generally comprising at least one layer containing one that the distribution of the compound is brought into contact with the photographic recording materials, such as a halogenation according to an image of an electron donor compound and 45 silver, associated with a stationary compound. The expression that they are kept under conditions which allow the rearrangement "associated with" is used in photography and relates to this intramolecular nucleophilic arrangement, one obtains an immobile distributed compound which is in relation to the substance allows-tion according to an image of the liberated group. In case the count to obtain the photographic recording. We can apply-dye is a dye whose maximum absorption is offset, quer the respective substances in the same layers or in and which contains the releasable grouping, we obtain, by modifying 50 separate layers provided that they are associated and isolated cation absorption, a distribution according to an image presenting effectively to provide the desired reactions before a bathochromic shift or a hypsochromic shift to the significant liberation of products of intermediate reactions dif-ration of the grouping. fuse to adjacent recording layers.

In other embodiments, the compounds are used. The compounds according to the invention and their preparation are de-

according to the invention, to determine the presence and the content of 55 crits in the following examples. Releasable groups some reducing agents in a given medium. crits are mobile dyes useful in photography.

In other embodiments, the compounds are used In the synthesis of the compounds described in the examples according to the invention in a process, in stages, during which the following, the structure is confirmed in each case by analysis the compounds are reduced during the first stage without that infrared. In some cases an additional verification this modification is visible. Subsequent contact with a mid-60 is made by mass spectroscopy, and by NMR analysis. An alkaline place favors intramolecular nucleophilic rearrangement- specifies the melting points of the intermediates when this appears where the reduction takes place. brings something more to the identification of the compound-

The expression "indisputable" used in the description has the pectif.

The meaning usually given to this term and relates to the following examples illustrate the invention.

65

628,924

Example 1: Compound I

10

C12H25S02

S02C12H25

Step 1: 3,5-dichloro-2-nitrobenzoic acid

200 ml of 90% nitric acid are placed in a 5-liter flask with 3 tubes. The mixture is stirred and heated to 70 ° C. The heating jacket is removed and stirring continues. 500 g of solid 3,5-dichlorobenzoic acid are added in small portions in order to maintain the reaction temperature at 70 ° C. The reaction is very weakly exothermic so that fairly large amounts of 3,5-dichlorobenzoic acid can be added at one time. The total duration of the addition of the 500 g of acid takes place in approximately 20 minutes. After this addition, the reaction mixture is stirred and heated to 75-80 ° C for 3 h. Then the mixture is cooled (containing a part of the solid compound) and the cooling is finished in ice. The solid compound is collected on a sintered glass filter funnel and washed with cold water (3 times 500 ml) and then dried. 555.3 g of compound are obtained (yield 90%), the melting point of which is 190 ° -192 ° C.

Step 2: 3,5-didodecylthio-2-nitrobenzoic acid

A stream of nitrogen is passed, for 15 to 30 minutes, over a mixture consisting of 236 g (1 mole) of 3,5-dichloro -2-nitrobenzoic acid (step 1) and 424 g (2.1 moles) of 1-dodeca-nethiol in 1.51 ethanol and 11 water. Then 430 g (3.1 moles) of anhydrous potassium carbonate are added and the reaction mixture is heated under reflux under a nitrogen atmosphere, for 60 to 72 h. After having cooled to room temperature, the solution is slowly poured into a mixture, with rapid stirring, consisting of 61 of water, 360 ml of concentrated hydrochloric acid and crushed ice. The solid precipitate is collected and washed thoroughly with water. A paste of the yellow substance is formed using 2.71 glacial acetic acid, filtered, washed with a small amount of glacial acetic acid and dried under vacuum at 45 ° C. 560 g of product are obtained, the melting point of which is 74 ° C. to 77 ° C.

0 CH, n / a,

1 1

c-nch2ch2 <j-ch3

25

30

35

40

50

55

Step 3: 3,5-didodecylsulfonyl-2-nitrobenzoic acid

330 ml of 30% hydrogen peroxide are added to a paste subjected to stirring and consisting of 320 g (0.56 mole)

acid, 3,5-didodecylthio-2-nitrobenzoic acid (step 2) and 0.6 g (0.002 mole) of ethylenedinitrilotetraacetic acid in 2.61 glacial acetic acid. The mixture 60 is gradually heated to 75 ° C., then a slightly exothermic reaction takes place,

(giving a temperature close to 90 ° C). We stop heating when the exothermic reaction subsides. Then the test is heated to 80 ° C. until a negative or very weak control of peroxide is obtained using paper soaked in iodine and starch. At this point, 70 ml of 30% hydrogen peroxide are added all at once and the mixture is heated at 80 ° C. for 15 h. Desired white crystals crystallize on cooling and are collected and washed successively with glacial acetic acid and with water. Dry and 340 g of product are obtained, the melting point of which is 153 ° C.-155 ° C.

Step 4: 3,5-didodecylsulfonyl-2-nitrobenzoyl chloride Add 2 ml (0.16 mole) of oxalyl chloride and then 2 drops of N, N-dimethylformamide (DMF) to a paste containing 6.32 g ( 0.01 mole) of 3,5-didodecylsulfonyl-2-nitro-benzoic acid (step 3) in 50 ml of benzene. When the initial and rapid release of the gas has decreased, 6 drops of DMF are added in two batches. After 1 h, an additional 1 ml of oxalyl chloride is added. The reaction mixture is concentrated so as to obtain a yellow paste which is then triturated with 50 ml of cold acetonitrile. The mixture is filtered and washed with cold acetonitrile and a white solid is obtained. After drying in a vacuum oven, 4.81 g (74%) of the desired acid chloride are obtained.

Step 5: Compound I

A solution comprising 5.2 g (0.008 mole) of acid chloride (step 4) in 30 ml of tetrahydrofuran is added dropwise to a solution subjected to stirring and containing 5.7 g (0.008 mole) of 5- {3- [N- (methyl-aminoethyl) -N-methylsulfamoyI] phenylsuIfonamido} -4- (2-methylsulfonyl-4-nitrophenylazo) -1-naphthol hydrochloride in 50 ml of DMF containing 1, 7 g (0.0176 mole) of triethylamine. After this addition, most of the THF is removed in vacuo. The remaining solution is slowly poured into 250 ml of cold water and ice, which is stirred rapidly. A dark blue-black solid compound is collected and washed successively with water, then with dilute hydrochloric acid (0.01 N) and then with water. The washed substance is dried, dissolved in THF and poured into a 5 cm × 20 cm column filled with Florisil (activated magnesium silicate) of dimensions between 74 [d, and 148 [i. The product is eluted with 1500 ml of THF. The eluate is concentrated to dryness. The residue is dissolved in a minimum amount of dichloromethane and then poured slowly into 150 ml of ice-cold ligroin (melting point 35 ° C-60 ° C). The solid compound is collected, washed with ligroin and then dried. . 5.6 g (54%) of compound I are obtained.

11

628,924

Example 2: Compound II

c-nch2ch2ns02

0 CH.

cia «37 s02

- so2ch3

Step 1: 4-chloro-5-octadecy-sulfonyl-2-nitrobenzoic acid This compound is prepared from 4,5-dichloro-2-nitrobenzoic acid by the procedure described in steps 2 and 3 of the example 1; and using an equivalent of octadecane-thiol instead of dodecanethiol.

Step 2: 4-chloro-5-octadecylsulfonyl-2-nitroben-zoyl chloride

This compound is prepared from the free acid (step No. 1 above) and 16 equivalents of oxalyl chloride in accordance with the procedure of step No. 4 of Example 1.

30

Step 3: Compound II

The compound containing the corresponding dye is prepared by carrying out the process described in step No. 5 of Example 1 and using dye A and 4-chloro-5-octadecyl-sulfonyl-2-nitrobenzoyl chloride prepared at 1 'step 2 above.

Other nitroaryl derivatives and dyes are prepared and reacted together to form various aromatic nitro compounds according to the invention. The reactions and the conditions for preparing these compounds are described in Examples 1 and 2 below. The alkylenediamino group connecting the dye and nitrobenzoic acid is provided either (1) by reaction of the corresponding monoblock diamine and of the appropriate weighted nitrobenzoyl chloride, then by unblocking the amine and by reaction with a dye carrying a chloride group of sulfonyl or else (2) by reaction of an excess of a diamine and of a dye containing a chlorosulfonyl group then reaction of the resulting amino dye with the appropriate weighted nitrobenzoyl chloride. The compounds are prepared using the two classes of nitro derivatives and the appropriate classes of dye as given in Table I.

Table I Example

Compound

Nitrobenzene derivative

Coloring part

III

NO:

CiaHasSOa- "'^ J-COCI

Y

SOnCt 2Hü5

OH

f Y * T

Y Y

CHaSOcflH N = N

AT.

cha l ch3

I

• x ^ i-SOaNCaCHaNH'HCI

IV

NOa I

y * \

CiaHasSOz-j »N-COCI

Y

SO2C1sHas

(VS)

CH? I

CN I

no- <> - •.

"- • 11

Chai

not

. = 1

HCl • H NCHaCHa-N-SOa - “^

628924

Table I (continued)

Compound Example

12

Nitrobenzene derivative

Coloring part

V

NOa

AT

Ci zHssSOa-JJ NJ-C-n '\ -CHs

*\ AT " - '

0 NHE

T

SOaCi «Hcs

HCl

CN

(D) s-k "

N = N- <> -0C i I

f \ S \

\> -SO "CI}

VI

NO i

Ci p-HasSOs- "'% -C-N (CHr.) ANHa * HC I

\ / * "

T 0 '

SOaCiJHso

Chai

(D)

VII

NOa

CeHiTSOa- ”''% -COC I

Y

S 0 s: C 111 7

(AT)

(see step 5 of example I)

vni identical to example 7

(VS)

IX

NOa

5 'Ycocl Y

SOsCi9H37

(AT)

10

NOa

C1 eHa7S0a- | J / '^ J-COCI •> •

(AT)

11

XI

"0z CHa * N I

Ci 2HasS0s-J5 Xf-C-N (CHa) aNHz-HCI II

Y "

SOaCiaHa;

0

(E) H

O-C-CpHS

T * N * / ^? - S0? .NHC (CHa) a

NM N-N - "^ ^ • -SO -. 'CI I" r •

Sr.

I

CHi

13

628,924

Example 12 Preparation of Compound XII

0 II

o-c-%

V

r y nJ-S0enhc (CH2) a

S / 'y1

0 11

v - SOcNHCHn- ”. \ l-C \ # \ /.

NHSOsCHa / * =, \

Ci cHaoSOz - »^

-T

SOeCizHr

Step 1: 4-aminomethyl-1- (3,5-didodecylsulfonyl-2-nitrobenzoyl) piperidine hydrochloride

1.22 g (0.01 mole) of salicylic anhydride is added dropwise while stirring to 1.14 g (0.01 mole) of 4-aminome-thylpiperidine in 25 ml of benzene. Then, the volume is reduced to about 10 ml by distilling under atmospheric pressure to remove the benzene. The concentrated yellow solution is mixed with 30 ml of tetrahydrofuran (THF) and 1.01 g (0.01 mole) of triethylamine is added. The mixture is stirred and cooled in a cold water bath while a solution of 6.5 g (0.01 mole) of 3,5-didodécyIsuIfo-nyl-2- chloride is added dropwise. nitrobenzoyl (see example 1) in 40 ml of THF. After this addition, the reaction mixture is stirred for 30 min at room temperature and filtered to remove the by-product, triethylamine hydrochloride. The solid is washed with a small amount of THF and discarded. The filtrate is combined with washing with THF and this resulting solution is treated with 4 ml of 6N hydrochloric acid and the mixture is stirred for 15 h. The resulting gelled solution is boiled to reduce the volume of the acidified filtrate to about 50 ml. Next, the heated solution heated with 75 ml of acetonitrile is very slowly diluted and stirred rapidly. The diluted mixture is stirred at room temperature until it cools. A white solid compound is collected on a sintered glass funnel, washed with cold acetonitrile and dried. 4.69 g of the desired product are obtained. For a sample of the product, only one spot is obtained by thin layer chromatography on silica gel and using a mixture of methanol and acetone at 5 parts per 20 parts.

Step 2: Compound XII 20 15.3 g of 4-ami-nomethyl-1- (3,5-didodecylsulfonyl-2-nitrobenzoyl) piperidine hydrochloride are added, with stirring, to 300 ml of THF. When almost all of the hydrochloride is dissolved, 13.6 g of 4- [4-benzoyloxy-8-metha-nesulfonamido-3- (Nt-butylsulfamoyl) -l-naphthylazo] -benzè-nesulfonyl chloride are added, then added in small portions, 4 g of triethylamine, the viscosity of the mixture gradually decreases and stirring is continued at room temperature for 4 h, the mixture is filtered and the solid collected is discarded, the filtrate is chromatographed using 500 g of Florisil and taking as eluent a mixture consisting of two volumes of benzene for one volume of ethyl acetate. 18 g of a crude product are obtained. This product is dissolved in 100 ml of ethyl acetate, filtered, diluted to 450 ml with ether, left to stand for 15 hours, the solid formed is collected on a sintered funnel and washed with a constituted solution. 1 volume of ethyl acetate per 3.5 volume of ether and dried in vacuo at room temperature. 13.5 g of compound XII are collected.

30

35

40

Examples 13 to 15 The following compounds are prepared by the procedure described in Example 12 and using the appropriate intermediates.

Table II

Compound Example

13

XIII

I

"02 CHaCHaSOaNHs

At 1

CiaHasSOs- * nJ-C0N- * '•

"" * = T —v, ”- * v

) "- 0H CHsSOsNH -" ^ f

S0 ztlHC (CH.?) 3

Y

SO2C1sHs ç

NHSOr-

14

XIV

NOa

Ci aHssSOa —Nj> -C0N ^ ^ NSOa i. • I

T ^ • -nhsop .- "^

S0aCiaHc5 • s * ~ '\

N- <> -0H

. • - • N II

OaM - "^ ^> - N

'=!

SOCHA

628,924

14

Table II (continued)

Compound Example

15

XV

0 II

OC-CeHs

\ / ^ / \ r - N - SOp.NHC (CH.T),

r ^ ~ i vV

T T X # = V n /

CHsSOsNH N = n- »C> -SOcN (CHa) îiNCO - * ^

MO a

SO = Ci ri! - "I

"V

NOT"-"'

CHs

N # = r '

SOpC t pHps

Example 16

Photographic product giving a single color image and containing a compound substituted by a nitro radical and an incorporated electron donor compound.

A photographic product for diffusion-transfer is prepared by applying the following layers to a support of polyethylene terephthalate:

Layer 1 Negative silver bromide emulsion (0.8 | i) containing 1.08 g / m2 silver, 1.61 g / m2 gelatin, 044 g / m2 compound VII, 1.18 g / m2 diethyllauramide and 0.74 g / m2 of electron donor compound E - 1; and

Layer 2 0.54 g / m2 of tanned gelatin.

A sample of the product is exposed through a sensitometric range and treated, at 24 ° C., with a treatment solution contained in a frangible capsule containing 85 g of potassium hydroxide, 20 g of potassium bromide, 3 g of methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 1.0 g of 5-methyl-benzotriazole and 40 g of carboxymethylcellulose per 1 liter of water, and they are brought into contact with a receptor element containing 2.15 g / m2 of a copolymer of styrene and chloride of N, N, N-tri-n-hexyl-N-vinylbenzylammonium and 2.15 g / m2 of gelatin.

After 10 min, the photosensitive element is separated from the receiving element, a positive blue-green image of good definition is obtained on the receiver (Dmax: 2.0, Dmin: 0.18).

Example 17

Another photographic product giving an image with a single color is prepared by the procedure of Example 16, but the electron donor compound E - 1 is replaced by 0.27 g / m2 of electron donor compound E - 2, and the content of diethyllauramide is reduced from 1.18 g / m2 to 0.71 g / m2.

A sample of this product is exposed and treated according to the procedure described in Example 16. After 5 minutes, the elements are separated and an image of blue-green dye of good definition is obtained on the receiving element (Dmax : 1.28, Dmin: 0.18).

Example 18

Compound substituted by a nitro radical forming a single color and electron donor compound incorporated in the treatment composition.

A photographic product of the following structure is prepared:

Layer 1 Polyethylene terephthalate support;

Layer 2 Silver bromide emulsion (0.8 | i) containing 1.08 g / m2 of silver, 1.61 g / m2 of gelatin, 0.44 g / m2 of compound VII and 0.44 g / m2 of diethyllauramide; and

Layer 3 0.51 g / m2 of tanned gelatin.

A sample of the product is exposed through a sensitometric range and it is treated, at 24 ° C., with a treatment composition contained in a frangible capsule consisting of 51 g of sodium hydroxide, 20 g of potassium bromide, 0.5

g of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 3.0 g of N-methyl-5,7-dicarboxy-2, l-benzisoxazoIone and 40 g of carboxymethylcellulose per 1 liter of water, then they are brought into contact with a receiving element as described in Example 16. After 5 minutes, the elements are separated and a positive image of blue-green dye of good definition is obtained on the receiving element (Dmax: 1 , 01, Dmin: 0.30).

Example 19

25 A three-color image product containing compounds substituted by a nitro radical and precursors of incorporated electron donor compounds.

A photosensitive element used in diffusion-transfer, with several layers and with several colors, of the following structure is prepared:

Layer 1 A cellulose acetate support;

Layer 2 A silver bromoiodide emulsion sensitive to red (0.8 p) and containing 1.08 g / m2 of silver, 2.15 g / m2 of gelatin, 0.42 g / m2 of compound 1.0 , 63 g / m2 of electron donating compound E-1 and 1.05 g / m2 of 2,4-di-n-amyl-phenol;

Layer 31.61 g / m2 gelatin, 0.32 g / m2 dye. magenta filter and 0.22 g / m2 of 2,5-di-sec-dodecylhydroquinone and 0.16 g / m2 of diethyllauramide;

Layer 4 Silver bromoiodide emulsion sensitive to 40 green (0.8 (x) containing 1.61 g / m2 of silver, 3.22 g / m2 of gelatin, 0.70 g / m2 of compound XII, 1 , 27 g / m2 of electron donor compound E-1 and 1.97 g / m2 of 2,4-di-n-amyl-phenol;

Layer 5 2.15 g / m2 gelatin, 1.08 g / m2 yellow filter dye, 0.22 g / m2 2,5-di-sec-dodecylhydroquinone and 45 0.54 g / m2 diethyllauramide ;

Layer 6 Blue bromoiodide emulsion sensitive to blue (0.8 n) containing 1.61 g / m2 g / m2 of silver, 3.22 g / m2 of gelatin, 0.58 g / m2 of compound VI, 1.32 g / m2 of an electron donor compound E - 1 and 1.89 g / m2 of 2,4-di-n-amyl-phe-50 noi; and

70.86 g / m2 layer of tanned gelatin.

A sample of the product is exposed to a white light source and to selectively filtered light sources 55 and consisting of red, green, blue, blue-green, magenta and yellow, each being focused on a separate part of the photosensitive element .

The exposed sample is treated at 24 ° C., bringing it into contact with a composition contained in a frangible 60 capsule containing 51 g of potassium hydroxide, 20 g of potassium bromide, 3.0 g of 4 -methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 2.0 g of 5-methylbenzotriazole and 40 g of carboxymethylcellulose per 1 liter of water, then they are brought into contact with a receptor element comprising 2.15 g / m2 of the 65 copolymer of styrene and chloride of N, N, N-tri-n-hexyl-N-vinylbenzylammonium and 2.15 g / m2 of gelatin.

After 10 min, the photosensitive element and the receiving element are separated and the densities of

15

628,924

dye transferred, by reflection, and the following results are obtained:

Dye density by reflection

Exposure

Red

Green

Blue none

1.86

1.54

1.64

white

0.28

0.41

0.36

yellow

0.30

0.52

1.24

magenta

0.44

1.18

0.60

Blue green

1.78

0.75

0.56

red

0.41

1.30

1.52

green

1.78

0.86

1.39

blue

1.93

1.50

0.82

Example 20

A photosensitive element is prepared by applying to a support of polyethylene terephthalate, a layer containing 2.16 g / m2 of gelatin, a negative silver bromide emulsion containing 1.08 g / m2 of silver, 3.78 X 10 "4 moles / m2 of a nitro aromatic compound and 7.56 X 10" 4 moles / m2 of a hydrolysable electron donor compound. The nitro aromatic compound and the electron donor compound are dissolved in an equal mass of diethyllauramide and dispersed in gelatin before applying as a layer. Next, a suitable tanned overcoat containing 0.86 g / m2 gelatin is applied.

The samples of the element are exposed according to an image through a sensitometric range and they are treated at 24 ° C., with viscous treatment compositions contained in frangible capsules constituted by 51 g of potassium hydroxide, 20 g of bromide. potassium, 3.0 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 51 g of carboxymethylcellulose and 1.0 g of 5-methylbenzotriazole per 1 liter of water, then they are brought into contact with a receptor element containing a polymeric mordant, the copolymer of divinylbenzene, styrene and chloride of N-benzyl-N, N-dimethyl-N-vinylbenzylammonium. After 10 min, the photosensitive elements and the receiving elements are separated and a positive image of good definition is observed on each receiving element. The minimum and maximum densities 4 <> are measured at the appropriate light sources of each dye image and they are listed in the following table:

Layer 4 Blue-green dye-forming layer, sensitive to red, containing a negative emulsion of silver bromoiodide sensitive to red, containing 1.08 g / m2 of silver, 0.42 g / m2 of compound 1.0, 64 g / m2 of electron donor compound E 5 - 1.16 g / m2 of 2,4-di-n-amylphenol and 2.16 g / m2 of gelatin;

Layer 5 Interlayer containing 1.62 g / m2 of gelatin, 0.22 g / m2 of 2,5-di-sec-dodecylhydroquinone, 0.16 g / m2 of diethyllauramide and a magenta filter dye;

Layer 6 Magenta dye-forming layer, green-sensitive 10, containing a silver bromoiodide negative emulsion, green-sensitive, and containing 1.62 g / m2 silver, 0.67 g / m2 of compound XV, 1 , 22 g / m2 of electron donor compound E - 1,1,89 g / m2 of 2,4-di-n-amylphenol and 3.24 g / m2 of gelatin;

Layer 7 Interlayer containing 2.16 g / m2 of gelatin, 0.22 g / m2 of 2,5-di-sec-dodecylhydroquinone and a yellow filter dye;

Layer 8 Yellow dye-forming layer, sensitive to blue, containing a negative emulsion of silver bromoiodide, sensitive to blue, and containing 1.62 g / m2 of silver, 0.58 g / m2 of compound VI , 1.32 g / m2 of electron donor compound E - 1.18 g / m2 of 2,4-di-n-amylphenol and 3.24 g / m2 of gelatin;

30

35

Compound Element Compound 5-methyl-

Benzotri donor number

of azole electrons

No (g / 1)

Dmax Dmin

45

50

A B

XIII

XIV

E —5 E-5

1.65 2.26

0.16 0.14

Example 21

Inseparable product, giving a three-color image by diffusion-transfer and containing a receiving element and method of implementation.

An inseparable product containing an image receptor is prepared by applying the following layers to the support of polyethylene terephthalate in the order mentioned:

Layer 1 Receiving layer containing 2.16 g / m2 of gelatin, 2.16 g / m2 of the copolymer of styrene, of N, N, N-tri-n-hexyl-N-vinylbenzylammonium chloride;

Layer 2 White reflective layer containing 3.89 g / m2 of gelatin and 21.6 g / m2 of titanium dioxide;

Layer 3 Opaque layer containing 2.7 g / m2 of gelatin and 1.62 g / m2 of carbon black;

55

60

Layer 9 Tanned overcoat containing 0.86 g / m2 of gelatin.

A sample of the photographic product prepared above is selectively exposed through a multicolored sensitometric range comprising filtered white, red, green, blue, blue-green, magenta and yellow light sources, each being focused on a determined part of the product.

The exposed sample is treated at 24 ° C. by applying an additional treatment sheet and a frangible capsule containing a viscous treatment solution consisting of 51 g of potassium hydroxide, 20 g of potassium bromide 3.0 g of 4 -hydroxymethyl-4-methyl-1-phenyl-3-pyrazoIidone, 2.0 g of 5-methylbenzotriazole, 51 g of carboxymethylcellulose per 1 liter of water.

The complementary sheet consists of a support of polyethylene terephthalate to which is applied:

1) a layer of a copolymer of butyl acrylate and acrylic acid;

2) a first retarding layer containing a mixture of cellulose acetate and a copolymer of styrene and maleic anhydride;

3) a second retarding layer containing a dispersion of a copolymer of acrylonitrile, vinylidene chloride and acrylic acid.

In addition, an opaque backing sheet is applied to the face opposite the complementary sheet to allow treatment in ambient light.

After 15 min, the densities in red, green and blue lights are measured and the results are listed in the following table.

65

Density by reflection

Exposure

Red

Green

Blue blue-green

1.30

0.50

0.45

magenta

0.34

1.40

0.65

yellow

0.18

0.46

1.75

white

0.18

0.35

0.48

red

0.36

1.62

1.95

green

1.72

0.60

1.85

blue

2.00

1.85

0.85

any

1.80

1.76

1.93

628,924

In the examples above, good results are obtained when a transparent complementary sheet is used together with a treatment composition containing sufficient

sufficient carbon black to prevent harmful exposure to ambient light through the layer formed by the treatment composition.

VS

Claims (9)

628,924 2 CLAIMS 1. Chemical compounds characterized in that they have the following general formula: . - X. / Tr —Hz1 '"- y— •" (R) --r-— - q-x - p-X "i rn-l E-Q- - X in which A represents the atoms necessary to complete a mono- or polycyclic aromatic or hetero-aromatic group, the ring of which carries the nitro radical is penta-gonal or hexagonal; W represents an electron acceptor group; R2 represents a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms, an aryl radical of 6 to 30 carbon atoms; R1 represents a bivalent organic radical containing from 1 to 3 atoms in the bivalent linking chain; m and q are equal to 1 or 2; p is equal to or greater than 1, and p is equal to 1 only when A contains an aromatic onium radical, and when p is equal to 2, the substituent [(R2 - - W] is in the ortho or para position relative to the nitro radical; E and Q form a releasable electrophilic group where E represents an electrophilic center and represents a group forming a monoatomic link chain between E ex X1, Q representing an oxygen atom, a sulfur atom, an atom of selenium or a nitrogen atom; n is between 1 and 3; and X1 considered with Q, represents either a group forming a dye image, or a group of a photographic reagent. 2. Chemical compounds according to claim 1, characterized in that they have the following formula: selenium or a nitrogen atom which forms an amino radical; and X1 represents either a dye-forming group or a group of a photographic reagent. 3. Chemical compounds according to one of claims 1 and 2, characterized in that they have the following formula: E-Q-X 20 25 U R2> -y./ "Vszr * -" - * 1 35 40 in which q and m are equal to 1 or 2 and p is equal to 3.4 or 5 W represents an electron acceptor group; R2 represents an alkyl radical containing 1 to 20 carbon atoms, an aryl group containing 6 to 30 carbon atoms; R1 represents a bivalent organic radical containing 1 to 3 atoms in the bivalent link chain 45; E and Q form a releasable electrophilic group where E represents an electrophilic center such as a carbonyl, sulfonyl radical, and Q represents a group forming a monoatomic link chain between E and X1, and Q represents an oxygen atom, a sulfur atom, a 50 atom in which p is an integer between 1 and 5; W represents an electron acceptor group; R2 represents an alkyl radical containing 1 to 20 carbon atoms, an aryl radical of 6 to 30 carbon atoms; E and Q form a releasable electrophilic group where E represents an electrophilic center such as a carbonyl or sulfonyl radical, and Q represents a group forming a monoatomic bond chain between E and X1, Q represents an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom; and X1 represents a dye-forming group or a group of a photographic reagent. 4. Chemical compounds according to one of claims 1 to 3, characterized in that, in the formula, Q-X1 represents a dye image-forming group and advantageously an azo dye-forming group. 5. Chemical compounds according to one of claims 1 to 4, characterized in that, in the formula, E represents a carbonyl group. 6. Chemical compounds according to one of claims 1 to 5, characterized in that, in the formula, p represents an integer between 2 and 5 and A completes an aromatic carbocyclic group. 7. Chemical compounds according to one of claims 1 to 6, characterized in that, in the formula, p and equal to 3, one of the groups represented by W is a bivalent sulfonyl radical and one of the groups represented by W is a monovalent electron accepting group. 8. Chemical compounds according to one of claims 1 to 7, characterized in that, in the formula, W represents a sulfonyl radical, p is equal to 3 and q is equal to 2. 9. Chemical compounds according to one of claims 1 to 8, characterized in that they are chosen from the compounds corresponding to the following formulas: yV 0 CHa Il I J! f-SOzNH V S0s I OH l A 1 f Ci aHaBSOs-Jj f-C-NCHaCHaN-CHa * \ ✓ • -NOs SOaCiaHas N = N AT • t " I 'I Y N'Oz SO2CH3 628,924 0 II o-c- #; NOT s f o it ' .iN 7 H VS0.NHC (CH ”) a Y'Y I T / * = * \ / • "• s I N = N- "X> -SOaNHCHa-" ') N-C CieHasSOa - "^% -NOa -T SOsCi2Has NHSOsCHs